CN106832260A - A kind of degradable antibacterial polyaminoacid and preparation method thereof - Google Patents
A kind of degradable antibacterial polyaminoacid and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
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- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
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Abstract
The present invention discloses a kind of degradable antibacterial polyaminoacid, and the polyaminoacid has following structure：
Description
Technical field
The present invention relates to anti-biotic material field.More particularly, to a kind of degradable antibacterial polyaminoacid and its preparation side
Method.
Background technology
With the improvement of people ' s living standards, either in daily life, or in health care, people are to antibacterial
The demand of material gradually increases.Realize under increasingly enhanced background to human health, environmental protection and conservation culture simultaneously, resist
The development of bacterium material no longer simply considers anti-microbial property, also to consider that material will to the friendly of environment and the security of human body
Ask.At present, anti-biotic material is broadly divided into antimicrobial coating and body addition anti-biotic material.Antimicrobial coating is by suppressing bacterium in material
The initial formation sticked and then suppresses plaque bio-film on surface, but with coating shedding, be difficult to degrade, toxic side effect etc. is consolidated
Some limitations.Body adds anti-biotic material makes it have anti-microbial property by adding antiseptic, but there is material property decline, resists
The defects such as microbial inoculum is easily separated out, antimicrobial long-acting difference.Therefore, material has certain anti-microbial property in itself, while taking into account good
Biocompatibility and degradation property, the key as anti-biotic material.
Polyaminoacid class material possesses good biocompatibility, biological degradability etc. because of the structure of its analogous protein
Advantage, is widely used to the biologic medical such as medicine controlled releasing, organizational project, gene therapy field.At present, with microbial fermentation system
Standby polyaminoacid has gamma-polyglutamic acid and epsilon-polylysine, although amount is big pollution-free, but molecular weight of product is excessive, be distributed
Width, not easy purification；There are the homogeneous polyamino acids such as poly-aspartate, polyglutamic acid with polyaminoacid prepared by chemical synthesis.
Therefore, it is the range of application of expansion polyaminoacid, assigns its new advantage or characteristic, can be by introducing two kinds of differences
The species of performance (hydrophobicity, hydrophily) amino acid monomer, ratio and content control the performance of polyaminoacid, to design system
It is standby that there is anti-microbial property, good biocompatibility and degradation property etc. to have both multi-functional material.
The content of the invention
It is an object of the present invention to provide a kind of degradable antibacterial polyaminoacid, the polyaminoacid has itself in itself
Certain anti-microbial property, while taking into account good biocompatibility and degradation property.
It is another object of the present invention to provide a kind of method for preparing above-mentioned degradable antibacterial polyaminoacid.
To reach above-mentioned purpose, the present invention uses following technical proposals：
A kind of degradable antibacterial polyaminoacid, the polyaminoacid has following structure：
It is abbreviated as [(A) m- (B) n] z；
Wherein,
M and n are respectively the number of repeat unit of component polyaminoacid repeat unit A and B；
Z is the number of repeat unit of (A) m- (B) n；
M, n, z are positive integer, m=10-10000, n=0-1000, z=1-10.
Further, the amino acid A contains the alpha amino acid of two or more amino for molecular structure, includes without
It is limited to lysine, histidine, ornithine etc..Positively charged because it contains free amino, its effect is regulation polyaminoacid material
Expect the anti-microbial property of performance；
The amino acid B be hydrophobicity alpha amino acid or hydrophily alpha amino acid, include, without being limited to alanine, valine,
Serine, threonine, aspartic acid, glutamic acid etc..Hydrophilicity and degradability its role is to adjust polyaminoacid material
Energy.
A kind of preparation method of degradable antibacterial polyaminoacid, including：
(1) polymerisation：By carboxylic acid in carboxylic acid anhydrides in initiator, the amino acid A-N- with protection group or amino acid A-N-
Acid anhydride is dissolved in organic solvent X successively, and the polymerisation of amino acid A is carried out under nitrogen protection, is subsequently adding in amino acid B-N-
Carboxylic acid anhydrides, carries out the polymerisation of amino acid B, after reaction terminates, solution decompression concentration is removed into solvent, by the solution after concentration
Precipitated in ether, drying obtains polyaminoacid or polyaminoacid with protection group；
(2) deprotection reaction：Polyaminoacid with protection group organic solvent Y is dissolved, is protected and is kept away in nitrogen
Deprotection agent is added under optical condition, is reacted, product ether sedimentation, filtering, washing is dried, and is obtained final product.
Further, the organic solvent X is DMF, DMA, dioxane, diformazan
One or more mixture in base Asia maple, tetrahydrofuran；Preferably, the organic solvent is N, N- dimethyl formyls
Amine.
Further, the initiator is any one in primary amine, secondary amine；Wherein, the primary amine be triethylamine, n-butylamine,
N-hexylamine, lauryl amine, tetradecy lamine, cetylamine, octadecylamine, propargylamine, 3- aminopropyl triethoxysilanes, N- (2- aminoethyls)-
In 3- aminopropyl triethoxysilanes any one；The secondary amine is 1,1,1- trimethyl-N-2- propylene propylamine base silane, pregnancy
In the silicon amine of base two any one.
Further, carboxylic acid anhydrides draws with described in carboxylic acid anhydrides or amino acid A-N- in the amino acid A-N- with protection group
The mol ratio for sending out agent is 10-10000:1；Carboxylic acid anhydrides and the mol ratio of the initiator are 10-1000 in the amino acid B-N-:
1。
Further, carboxylic acid anhydrides includes but is not limited to N in the amino acid A-N- with protection group6- benzyloxycarbonyl group-L- relies
Carboxylic acid anhydrides, N in propylhomoserin-N-6Carboxylic in carboxylic acid anhydrides, N'- benzyloxycarbonyl groups-L-Orn-N- in-tertbutyloxycarbonyl -1B-N-
Carboxylic acid anhydrides in acid anhydrides, N'- (2- benzyloxycarbonylchlorides base)-L-Orn-N-, carboxylic acid anhydrides is included but is not limited in the amino acid A-N-
Carboxylic acid anhydrides in histidine-N-；Carboxylic acid anhydrides includes but is not limited to carboxylic acid anhydrides in alanine N-, valine N- in the amino acid B-N-
Carboxylic acid anhydrides, glutamic acid N-interior carboxylic acid in carboxylic acid anhydrides, aspartic acid N- in carboxylic acid anhydrides, threonine N- in interior carboxylic acid anhydrides, serine N-
Acid anhydride.
It should be noted that lysine contains two-NH with ornithine2, in order that-the NH of α2Reaction is participated in, another
- the NH of position2Need to be protected in advance, form carboxylic acid anhydrides in the amino acid A-N- with protection group；Contain in the structure of histidine
There is-a NH2With-a NH- ,-NH2It is more active than-NH-, reaction is first participated in, therefore degradable antibacterial is being prepared using histidine
Polyaminoacid without additionally introducing blocking group, i.e., without carrying out deprotection reaction.
Further, in step (1), the polymeric reaction temperature of the amino acid A is 10-100 DEG C, and the time of reaction is 12-
72h；The polymeric reaction temperature of the amino acid B is 10-100 DEG C, and the time of reaction is 12-48h.
Polymerization reaction time of the present invention is too short to cause carboxylic acid anhydride reactant in amino acid-N- incomplete, the polyaminoacid for obtaining
The degree of polymerization it is relatively low；Reaction time is long so that the polyaminoacid degree of polymerization and polydispersity index are too high, causes its stability and pure
Degree is reduced.
Further, in step (2), the organic solvent Y is dichloromethane or trifluoroacetic acid；
When organic solvent Y is dichloromethane, the deprotection agent can be Iodotrimethylsilane, trim,ethylchlorosilane or three
Methyl bromo-silicane, the temperature of the reaction is 20-40 DEG C, and the reaction time is 12-36h, it is preferred that the temperature of the reaction is 35
DEG C, the reaction time is 20h；
When organic solvent Y is trifluoroacetic acid, the deprotection agent can be 33% hbr/acetic acid mixed solution；Institute
The temperature of reaction is stated for 20-40 DEG C, the reaction time is 1-3h, it is preferred that the temperature of the reaction is 35 DEG C, the reaction time is
2h。
Further, the drying is to be vacuum dried 18-36h at freeze-drying or 20-40 DEG C；Preferably, it is true at 25 DEG C
Sky dries 24h.
Beneficial effects of the present invention are as follows：
(1) polyaminoacid of the present invention has good biocompatibility and anti-microbial property, and can voluntarily degrade in vivo
Into amino acid monomer, have no toxic side effect.
(2) present invention is by changing the factors such as amino acid classes, amino acid ratio and initiator content, is prepared for having
Anti-microbial property, good biocompatibility and degradation property etc. have both multi-functional material.
Specific embodiment
In order to illustrate more clearly of the present invention, with reference to preferred embodiment, the present invention is described further.Ability
Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, and should not limit this with this
The protection domain of invention.
A kind of preparation method of degradable antibacterial polyaminoacid of embodiment 1
(1) polymerisation：Respectively by 0.01moL N6Carboxylic acid anhydrides, 0.001moL draw in-benzyloxycarbonyl group -1B-N-
Hair agent hmds is in molar ratio 10:1 is dissolved in the anhydrous DMFs of 20mL successively, and 10 DEG C in nitrogen
Under protection, 12h is reacted.After reaction terminates, solution decompression is distilled off solvent, then the solution after concentration sinks in ether
Form sediment, vacuum drying obtains the polyaminoacid with protection group.
(2) deprotection reaction：Polyaminoacid with protection group 5mL trifluoroacetic acids are dissolved, then in stirrer
Stirring is lower to add the hbr/acetic acid mixed solution that 5mL hydrogen bromide mass contents are 33%, 1h is reacted at 20 DEG C, product
Settled with ether, filtering, washing, freeze-drying 18h obtains the polyaminoacid of deprotection.
Polyaminoacid number-average molecular weight obtained in the present embodiment is 5210, and weight concentration is 5% polyaminoacid material pair
1.0 × 10 in normal saline solution5After the Escherichia coli of cfu/mL concentration act on 24 hours, bacterial concentration reduces more than 50%；
It is non-toxic to l cell L929.
A kind of preparation method of degradable antibacterial polyaminoacid of embodiment 2
(1) polymerisation：Carboxylic acid anhydrides, 0.01mmoL in 0.01moL N'- benzyloxycarbonyl groups-L-Orn-N- are drawn respectively
Hair agent n-butylamine is in molar ratio 1000:1 is dissolved in the anhydrous DMAs of 20mL successively, and 20 DEG C are protected in nitrogen
Under, react 36h.After reaction terminates, solution decompression is distilled off solvent, then the solution after concentration is precipitated in ether,
Vacuum drying obtains the polyaminoacid with protection group.
(2) deprotection reaction：The polyaminoacid that protection group will be carried is dissolved with 20mL dichloromethane, in nitrogen atmosphere and
0.5mL Iodotrimethylsilanes are added under the conditions of lucifuge, 21h is reacted at 30 DEG C, product is settled with petroleum ether, filtering, with anhydrous
Ether and substantial amounts of deionized water are washed, and freeze-drying 36h obtains the polyaminoacid of deprotection.
Polyaminoacid number-average molecular weight obtained in the present embodiment is 81832, and weight concentration is 3% polyaminoacid material pair
3.2 × 10 in normal saline solution5After the Escherichia coli of cfu/mL concentration act on 24 hours, bacterial concentration reduces more than 50%；
It is non-toxic to l cell L929.
A kind of preparation method of degradable antibacterial polyaminoacid of embodiment 3
Polymerisation：Respectively by carboxylic acid anhydrides, 0.001mmoL initiators n-hexylamine in 0.01moL histidines-N- in molar ratio
It is 10000:1 is dissolved in 20mL DMFs successively, and 30 DEG C under nitrogen protection, reacts 72h；Reaction terminates
Afterwards, solution decompression is distilled off solvent, then the solution after concentration is precipitated in ether, vacuum drying obtains poly- amino
Acid.
Polyaminoacid number-average molecular weight obtained in the present embodiment is 154317, and weight concentration is 1% polyaminoacid material
To in normal saline solution 4.8 × 105After the staphylococcus aureus of cfu/mL concentration acts on 24 hours, bacterial concentration is reduced
More than 50%；It is non-toxic to l cell L929.
A kind of preparation method of degradable antibacterial polyaminoacid of embodiment 4
(1) polymerisation：By 0.01moL N6Carboxylic acid anhydrides and 1mmoL initiator alkynes in-benzyloxycarbonyl group -1B-N-
Propylamine, in molar ratio be 100:1 is dissolved in 20mL V (anhydrous N,N-dimethylformamide)：V (tetrahydrofuran)=4:In 1,25 DEG C
Under nitrogen protection, 24h is reacted, carboxylic acid anhydrides in 1mmoL alanine-N- is added, 48h is reacted.After reaction terminates, solution is subtracted
Pressure is distilled off solvent, and then the solution after concentration is precipitated in ether, and vacuum drying obtains the poly- amino with protection group
Acid.
(2) deprotection reaction：Polyaminoacid with protection group 5mL trifluoroacetic acids are dissolved, then in stirrer
Stirring is lower to add the hbr/acetic acid mixed solutions of 5mL 33%, and 2h is reacted at 35 DEG C, and product is settled with ether, and filtering is washed
Wash, 24h is vacuum dried at 30 DEG C, obtain the polyaminoacid of deprotection.
Polyaminoacid number-average molecular weight obtained in the present embodiment is 19819, and weight concentration is 4% polyaminoacid material pair
1.9 × 10 in normal saline solution5After the staphylococcus aureus of cfu/mL concentration acts on 24 hours, bacterial concentration reduces 50%
More than；It is non-toxic to l cell L929.
A kind of preparation method of degradable antibacterial polyaminoacid of embodiment 5
(1) polymerisation：Carboxylic acid anhydrides in 0.01moL N'- benzyloxycarbonyl groups-L-Orn-N- is drawn with 0.01mmoL respectively
Hair agent 1,1,1- trimethyl-N-2- propylene propylamine base silane is in molar ratio 1000:1 is dissolved in the anhydrous N of 20mL, N- dimethyl formyls
In amine, 30 DEG C under nitrogen protection, reacts 36h, adds carboxylic acid anhydrides in 0.001moL valines-N-, reacts 24h；First afterwards
After be alternately added 0.01moL N6Carboxylic acid in carboxylic acid anhydrides and 0.001moL valines-N- in-(benzyloxycarbonyl group) -1B-N-
Acid anhydride 4 times.After reaction terminates, solution decompression is distilled off solvent, then the solution after concentration is precipitated in ether, vacuum is dried
It is dry to obtain the polyaminoacid with protection group.
(2) deprotection reaction：Polyaminoacid with protection group 5mL trifluoroacetic acids are dissolved, then in stirrer
The hbr/acetic acid mixed solution of the lower addition 5mL 33% of stirring, reacts 3h at 30 DEG C, and product is settled with ether, filtering,
Washing, 36h is vacuum dried at 40 DEG C, obtains the polyaminoacid of deprotection.
Polyaminoacid number-average molecular weight obtained in the present embodiment is 60103, and weight concentration is 3% polyaminoacid material pair
1.0 × 10 in normal saline solution5After the Escherichia coli of cfu/mL concentration act on 24 hours, bacterial concentration reduces more than 50%；
It is non-toxic to l cell L929.
A kind of preparation method of degradable antibacterial polyaminoacid of embodiment 6
Polymerisation：Respectively by carboxylic acid anhydrides, 0.0001moL initiator triethylamines in 0.01moL histidines-N- in molar ratio
It is 100:1 is dissolved in 50mL anhydrous tetrahydro furans successively, and 35 DEG C under nitrogen protection, reacts 48h, adds 0.1moL figured silk fabrics ammonia
Carboxylic acid anhydrides in acid-N-, reacts 12h；Successively be alternately added afterwards carboxylic acid anhydrides and 0.1moL valines in 0.01moL histidines-N--
Carboxylic acid anhydrides 9 times in N-.After reaction terminates, solution decompression is distilled off solvent, then the solution after concentration sinks in ether
Form sediment, vacuum drying obtains polyaminoacid.
Polyaminoacid number-average molecular weight obtained in the present embodiment is 61784, and weight concentration is 3% polyaminoacid material pair
1.2 × 10 in normal saline solution5After the staphylococcus aureus of cfu/mL concentration acts on 24 hours, bacterial concentration reduces 50%
More than；It is non-toxic to l cell L929.
A kind of preparation method of degradable antibacterial polyaminoacid of embodiment 7
(1) polymerisation：Respectively by 0.01moL N6Carboxylic acid anhydrides, 0.001moL in-tertbutyloxycarbonyl -1B-N-
Initiator lauryl amine is in molar ratio 10:1 is dissolved in 50mL anhydrous tetrahydro furans successively, and 20 DEG C under nitrogen protection, reaction
24h.Carboxylic acid anhydrides in 0.01moL serines-N- is added, 12h is reacted, after reaction terminates, solution decompression solvent is distilled off,
Then the solution after concentration is precipitated in ether, vacuum drying obtains the polyaminoacid with protection group.
(2) deprotection reaction：The polyaminoacid that protection group will be carried is dissolved with 20mL dichloromethane, in nitrogen atmosphere and
0.5mL Iodotrimethylsilanes are added under the conditions of lucifuge, 12h is reacted at 20 DEG C, product is settled with petroleum ether, filtering, with anhydrous
Ether and substantial amounts of deionized water are washed, and 24h is vacuum dried at 25 DEG C, obtain the polyaminoacid of deprotection.
Polyaminoacid number-average molecular weight obtained in the present embodiment is 91258, and weight concentration is 2% polyaminoacid material pair
4.3 × 10 in normal saline solution5After the staphylococcus aureus of cfu/mL concentration acts on 24 hours, bacterial concentration reduces 50%
More than；It is non-toxic to l cell L929.
A kind of preparation method of degradable antibacterial polyaminoacid of embodiment 8
(1) polymerisation：Respectively by carboxylic acid anhydrides in 0.01moL N'- (2- benzyloxycarbonylchlorides base)-L-Orn-N-,
0.1mmoL initiators tetradecy lamine is in molar ratio 100:1 be dissolved in successively 50mL anhydrous dimethyls base Asia maple in, 30 DEG C nitrogen protect
Under shield, 36h is reacted, add carboxylic acid anhydrides in 0.05moL threonines-N-, react 48h.After reaction terminates, solution decompression is distilled
Solvent is removed, then the solution after concentration is precipitated in ether, vacuum drying obtains the polyaminoacid with protection group.
(2) deprotection reaction：The polyaminoacid that protection group will be carried is dissolved with 20mL dichloromethane, in nitrogen atmosphere and
0.5mL trim,ethylchlorosilanes are added under the conditions of lucifuge, 24h is reacted at 30 DEG C, product is settled with petroleum ether, filtering, with anhydrous
Ether and substantial amounts of deionized water are washed, and freeze-drying 24h obtains the polyaminoacid of deprotection.
Polyaminoacid number-average molecular weight obtained in the present embodiment is 114857, and weight concentration is 1% polyaminoacid material
To in normal saline solution 4.0 × 105After the staphylococcus aureus of cfu/mL concentration acts on 24 hours, bacterial concentration is reduced
More than 50%；It is non-toxic to l cell L929.
A kind of preparation method of degradable antibacterial polyaminoacid of embodiment 9
(1) polymerisation：Respectively by 0.01moL N6Carboxylic acid anhydrides, 0.02mmoL draw in-benzyloxycarbonyl group -1B-N-
Hair agent cetylamine is in molar ratio 500:1 is dissolved in 50mL anhydrous dioxanes successively, and 40 DEG C under nitrogen protection, reaction
60h, adds carboxylic acid anhydrides in 0.02moL aspartic acids-N-, reacts 36h.After reaction terminates, solution decompression is distilled off molten
Agent, then precipitates the solution after concentration in ether, and vacuum drying obtains the polyaminoacid with protection group.
(2) deprotection reaction：The polyaminoacid that protection group will be carried is dissolved with 20mL dichloromethane, in nitrogen atmosphere and
0.5mL bromotrimethylsilanes are added under the conditions of lucifuge, 36h is reacted at 40 DEG C, product is settled with petroleum ether, filtering, with anhydrous
Ether and substantial amounts of deionized water are washed, and 36h is vacuum dried at 30 DEG C, obtain the polyaminoacid of deprotection.
Polyaminoacid number-average molecular weight obtained in the present embodiment is 12796, and weight concentration is 1% polyaminoacid material pair
5.2 × 10 in normal saline solution5After the staphylococcus aureus of cfu/mL concentration acts on 24 hours, bacterial concentration reduces 50%
More than；It is non-toxic to l cell L929.
A kind of preparation method of degradable antibacterial polyaminoacid of embodiment 10
(1) polymerisation：Respectively by 0.01moL N6Carboxylic acid anhydrides, 0.01mmoL in-tertbutyloxycarbonyl -1B-N-
Initiator octadecane is in molar ratio 1000:1 is dissolved in the anhydrous DMAs of 20mL successively, and 60 DEG C are protected in nitrogen
Under shield, 48h is reacted, add carboxylic acid anhydrides in 0.01moL glutamic acid-N-, react 24h.After reaction terminates, solution decompression is distilled
Solvent is removed, then the solution after concentration is precipitated in ether, vacuum drying obtains the polyaminoacid with protection group.
(2) deprotection reaction：Polyaminoacid with protection group 5mL trifluoroacetic acids are dissolved, then in stirrer
Stirring is lower to add the hbr/acetic acid mixed solutions of 5mL 33%, and 1h is reacted at 20 DEG C, and product is settled with ether, and filtering is washed
Wash, 24h is vacuum dried at 25 DEG C, obtain the polyaminoacid of deprotection.
Polyaminoacid number-average molecular weight obtained in the present embodiment is 104983, and weight concentration is 1% polyaminoacid material
To in normal saline solution 3.1 × 105After the Escherichia coli of cfu/mL concentration act on 24 hours, bacterial concentration reduce 50% with
On；It is non-toxic to l cell L929.
A kind of preparation method of degradable antibacterial polyaminoacid of embodiment 11
(1) polymerisation：Carboxylic acid anhydrides, 0.002mmoL in 0.01moL N'- benzyloxycarbonyl groups-ornithine-N- are triggered respectively
Agent 3- aminopropyl triethoxysilanes are in molar ratio 5000:1 is dissolved in the anhydrous DMFs of 20mL successively, and 80
DEG C under nitrogen protection, 48h is reacted, carboxylic acid anhydrides in 0.2mmoL alanine-N- is added, 24h is reacted.After reaction terminates, will be molten
Liquid vacuum distillation removes solvent, and then the solution after concentration is precipitated in ether, and vacuum drying obtains poly- with protection group
Amino acid.
(2) deprotection reaction：Polyaminoacid with protection group 5mL trifluoroacetic acids are dissolved, then in stirrer
Stirring is lower to add the hbr/acetic acid mixed solutions of 5mL 33%, and 2h is reacted at 30 DEG C, and product is settled with ether, and filtering is washed
Wash, 24h is vacuum dried at 25 DEG C, obtain the polyaminoacid of deprotection.
Polyaminoacid number-average molecular weight obtained in the present embodiment is 162980, and weight concentration is 1% polyaminoacid material
To in normal saline solution 7.0 × 105After the staphylococcus aureus of cfu/mL concentration acts on 24 hours, bacterial concentration is reduced
More than 50%；It is non-toxic to l cell L929.
A kind of preparation method of degradable antibacterial polyaminoacid of embodiment 12
Polymerisation：Respectively by carboxylic acid anhydrides, 0.001mmoL initiators N- (2- ammonia -4- second in 0.01moL histidines-N-
Base) -3- aminopropyl triethoxysilanes in molar ratio be 10000:1 is dissolved in the anhydrous DMAC N,N' dimethyl acetamides of 20mL successively
In, 100 DEG C are under nitrogen protection, react 72h, add carboxylic acid anhydrides in 0.001moL serines-N-, react 48h.Reaction terminates
Afterwards, solution decompression is distilled off solvent, then the solution after concentration is precipitated in ether, vacuum drying obtains poly- amino
Acid.
Polyaminoacid number-average molecular weight obtained in the present embodiment is 198283, and weight concentration is 1% polyaminoacid material
To in normal saline solution 7.2 × 105After the staphylococcus aureus of cfu/mL concentration acts on 24 hours, bacterial concentration is reduced
More than 50%；It is non-toxic to l cell L929；
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not right
The restriction of embodiments of the present invention, for those of ordinary skill in the field, may be used also on the basis of the above description
To make other changes in different forms, all of implementation method cannot be exhaustive here, it is every to belong to this hair
Obvious change that bright technical scheme is extended out changes row still in protection scope of the present invention.
Claims (10)
1. a kind of degradable antibacterial polyaminoacid, it is characterised in that the polyaminoacid has following structure：It is abbreviated as [(A) m- (B) n] z；
Wherein,
M and n are respectively the number of repeat unit of component polyaminoacid repeat unit amino acid A and amino acid B；Z is (A) m- (B) n's
Number of repeat unit；
M, n, z are positive integer, m=10-10000, n=0-1000, z=1-10.
2. polyaminoacid according to claim 1, it is characterised in that：The amino acid A for molecular structure contain two or
The alpha amino acid of two or more amino, can be lysine, histidine or ornithine；The amino acid B is hydrophobicity alpha amino acid
Or hydrophily alpha amino acid, can be alanine, valine, serine, threonine, aspartic acid or glutamic acid.
3. a kind of method for preparing polyaminoacid as claimed in claim 1 or 2, including：
(1) polymerisation：By carboxylic acid anhydrides in carboxylic acid anhydrides in initiator, the amino acid A-N- with protection group or amino acid A-N- according to
It is secondary to be dissolved in organic solvent X, the polymerisation of amino acid A is carried out under nitrogen protection, it is subsequently adding carboxylic acid in amino acid B-N-
Acid anhydride, carries out the polymerisation of amino acid B, after reaction terminates, solution decompression concentration is removed into solvent, by the solution after concentration in second
Precipitated in ether, drying obtains polyaminoacid or polyaminoacid with protection group；
(2) deprotection reaction：Polyaminoacid with protection group organic solvent Y is dissolved, in nitrogen protection and lucifuge bar
Deprotection agent is added under part, is reacted, product ether sedimentation, filtering, washing is dried, and is obtained final product.
4. method according to claim 3, it is characterised in that：The organic solvent X is N,N-dimethylformamide, N, N-
One or more mixture in dimethylacetylamide, dioxane, DMSO, tetrahydrofuran；Preferably, it is N,
Dinethylformamide.
5. method according to claim 3, it is characterised in that：The initiator is any one in primary amine, secondary amine；
Wherein, the primary amine is triethylamine, n-butylamine, n-hexylamine, lauryl amine, tetradecy lamine, cetylamine, octadecylamine, propargylamine, 3-
In aminopropyl triethoxysilane, N- (2- aminoethyls) -3- aminopropyl triethoxysilanes any one；The secondary amine is 1,1,
In 1- trimethyl-N-2- propylene propylamine base silane, hmds any one.
6. method according to claim 3, it is characterised in that：In the amino acid A-N- with protection group carboxylic acid anhydrides or
Carboxylic acid anhydrides and the mol ratio of the initiator are 10-10000 in amino acid A-N-:1；Carboxylic acid anhydrides and institute in the amino acid B-N-
The mol ratio for stating initiator is 10-1000:1.
7. method according to claim 3, it is characterised in that：Carboxylic acid anhydrides is in the amino acid A-N- with protection group
N6Carboxylic acid anhydrides, N in-benzyloxycarbonyl group -1B-N-6- carboxylic acid anhydrides, N'- benzyloxycarbonyl groups in tertbutyloxycarbonyl -1B-N- -
In L-Orn-N- in carboxylic acid anhydrides, N'- (2- benzyloxycarbonylchlorides base)-L-Orn-N- carboxylic acid anhydrides any one, the amino acid
Carboxylic acid anhydrides is carboxylic acid anhydrides in histidine N- in A-N-.
8. method according to claim 3, it is characterised in that：In step (1), the polymeric reaction temperature of the amino acid A
It it is 10-100 DEG C, the time of reaction is 12-72h；The polymeric reaction temperature of the amino acid B is 10-100 DEG C, the time of reaction
It is 12-48h.
9. method according to claim 3, it is characterised in that：In step (2), the organic solvent Y be dichloromethane or
Trifluoroacetic acid；
When organic solvent Y is dichloromethane, the deprotection agent can be Iodotrimethylsilane, trim,ethylchlorosilane or trimethyl
Bromo-silicane, the temperature of the reaction is 20-40 DEG C, and the reaction time is 12-36h, it is preferred that the temperature of the reaction is 35 DEG C,
Reaction time is 20h；
When organic solvent Y is trifluoroacetic acid, the deprotection agent can be 33% hbr/acetic acid mixed solution；It is described anti-
The temperature answered is 20-40 DEG C, and the reaction time is 1-3h, it is preferred that the temperature of the reaction is 35 DEG C, and the reaction time is 2h.
10. method according to claim 3, it is characterised in that：The drying is freeze-drying or dry in 20-40 DEG C of vacuum
Dry 24-36h；Preferably, it is vacuum dried 24h at 25 DEG C.
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